Marine Engineering College, Dalian Maritime University, Dalian 116026, China.
School of Resources and Environmental Sciences, XinJiang University, Wulumuqi 830000, China.
J Colloid Interface Sci. 2022 Feb 15;608(Pt 3):2718-2729. doi: 10.1016/j.jcis.2021.10.191. Epub 2021 Nov 5.
In this paper, sulfated ZrO were synthesized via precipitation and impregnation method, and the promoting effects of support sulfation on selective catalytic reduction (SCR) performance of CeO/ZrO catalysts were investigated. The results revealed that sulfated ZrO could significantly enhance the SCR activity of CeO/ZrO catalysts in a wide temperature range. Especially when S/Zr molar ratio was 0.1, CeO/ZrO-0.1S catalyst exhibited a large operating temperature window of 251 ∼ 500 °C and its N selectivity was 100 % in the temperature range of 150 ∼ 500 °C. Moreover, CeO/ZrO-0.1S catalyst possessed a superior low-temperature activity over 0.1S-CeO/ZrO catalyst. After exposing to 100 ppm SO for 15 h, a high NO conversion efficiency of CeO/ZrO-0.1S catalyst (90.7 %) could still be reached. The characterization results indicated that ZrO treated with a proper dosage of sulfate acid was beneficial to enlarge the specific surface area greatly. Sulfated ZrO was also in favor of promoting the transformation of CeO from crystalline state to highly-dispersed amorphous state, and inhibiting the transformation of ZrO from tetragonal to monoclinic phase. It could also enhance the total surface acidity greatly with an increase in both Brønsted acid sites and Lewis acid sites, thus significantly improving NH adsorption on catalyst surface. Besides, the promoting effect of support sulfation on SCR performance of CeO/ZrO catalysts was also related with the enhanced redox property, higher Ce/(Ce+Ce) ratio and abundant surface chemisorbed labile oxygen. The in-situ DRIFTS results implied that nitrate species coordinated on the surface of CeO/ZrO-0.1S catalyst could participate in the Selective catalytic reduction with ammonia (NH-SCR) reactions at either medium or high temperature, suggesting that both Eley-Rideal (E-R) and Langmuir-Hinshelwood (L-H) mechanisms might be followed in SCR reactions.
本文采用沉淀浸渍法合成了硫酸化 ZrO,并考察了载体硫酸化对 CeO/ZrO 催化剂选择性催化还原(SCR)性能的促进作用。结果表明,硫酸化 ZrO 能显著提高 CeO/ZrO 催化剂在较宽温度范围内的 SCR 活性。特别是当 S/Zr 摩尔比为 0.1 时,CeO/ZrO-0.1S 催化剂在 251500℃的操作温度窗口较大,在 150500℃的温度范围内,N 选择性为 100%。此外,CeO/ZrO-0.1S 催化剂在 0.1S-CeO/ZrO 催化剂上具有优异的低温活性。在暴露于 100ppm SO 15h 后,CeO/ZrO-0.1S 催化剂仍能达到较高的 NO 转化率(90.7%)。表征结果表明,用适量硫酸处理的 ZrO 有利于大大增加比表面积。硫酸化 ZrO 也有利于促进 CeO 从晶相向高分散无定形相的转变,并抑制 ZrO 从四方相到单斜相的转变。它还可以大大增强总表面酸度,增加 Brønsted 酸位和 Lewis 酸位,从而显著提高 NH 在催化剂表面的吸附。此外,载体硫酸化对 CeO/ZrO 催化剂 SCR 性能的促进作用也与增强的氧化还原性能、更高的 Ce/(Ce+Ce) 比和丰富的表面化学吸附的活性氧有关。原位 DRIFTS 结果表明,硝酸盐物种在 CeO/ZrO-0.1S 催化剂表面的配位可以在中温和高温下参与与氨(NH-SCR)的选择性催化还原反应,这表明在 SCR 反应中可能遵循 Eley-Rideal(E-R)和 Langmuir-Hinshelwood(L-H)两种机理。